Photoelectrochemical Hydrogen Production by a Cobalt Tetrapyridyl Catalyst Using Push–Pull Dye‐Sensitized NiO Photocathodes

Abstract

Herein, the synthesis and optoelectronic properties of a novel push–pull organic dye, pRK1, specifically designed for use in dye‐sensitized photocathodes for hydrogen generation, are reported. The chemical structure of this dye, which incorporates a benzothiadiazole moiety, is inspired by RK1, a dye previously reported as a photosensitizer in n‐type dye‐sensitized solar cells (DSSCs) with power conversion efficiencies above 10% and high stability. The photoelectrochemical activity for hydrogen evolution of pRK1 after grafting onto NiO photocathodes in combination with a cobalt tetrapyridyl catalyst [Co(bapbpy)(OH2)2](BF4)2 in aqueous solution is evaluated and compared with two reference dyes from the literature, RuP2‐bpy and P1. It is shown that among the three photocathodes studied in this work, NiO|pRK1 is the most efficient, producing up to 1.9 μmol cm−2 of hydrogen with a faradaic efficiency of 66%, under visible light irradiation in aqueous electrolyte at pH 4.5. pRK1 shows a turnover number (TONdye) of up to 145 during the 6 h chronoamperometric test, almost twice that of P1. This study demonstrates that the chemical structure of high performance dyes commonly used in DSSCs can be successfully modified to meet the requirements for light‐driven water splitting in dye‐sensitized photoelectrochemical cells.

Synthesis of Ru(ii) and Os(ii) photosensitizers bearing one 9,10-diamino-1,4,5,8-tetraazaphenanthrene scaffold

“…Similar approaches are used for CO 2 reduction, as well as for the development of photocathode or photoanode materials. 15,60–66 A general pattern in the photocatalysis approach is to connect a photosensitizer and catalytic centre via a bridging ligand. This allows for efficient electron or hole transfer and subsequent long-lived charge separated state, as well as the modification of the associated redox potential, which can tune the range and efficiency of possible transformations.…”